US9976223B2 - Nickel and/or chromium plated member and method for manufacturing the same - Google Patents

Nickel and/or chromium plated member and method for manufacturing the same Download PDF

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US9976223B2
US9976223B2 US14/737,102 US201514737102A US9976223B2 US 9976223 B2 US9976223 B2 US 9976223B2 US 201514737102 A US201514737102 A US 201514737102A US 9976223 B2 US9976223 B2 US 9976223B2
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layer
nickel
nickel layer
bright
plating
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US20160265131A1 (en
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Jingjun Hao
Liming Qian
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Jiaxing Minhui Automotive Parts Co Ltd
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Jiaxing Minhui Automotive Parts Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/625—Discontinuous layers, e.g. microcracked layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Definitions

  • the present invention relates to a work piece having an electroplating layer on its surface and a method for manufacturing the same, in particular, to a nickel and/or chromium plated member or a method for manufacturing the same.
  • the anti-corrosive capacity of a work piece could be improved by plating two or three layers of nickel and then plating chromium in the electroplating industry.
  • the widely applied two-layer nickel plating process includes plating Semi-bright nickel, bright nickel, and crack-free chromium.
  • the widely applied three-layer nickel plating process includes plating Semi-bright nickel, bright nickel, microporous nickel, and crack-free chromium or plating Semi-bright nickel, bright nickel, micro-crack nickel, and crack-free chromium.
  • a chromium plating layer without any cracks or pores in the industry, including a hexavalent chromium and a trivalent chromium plating layer.
  • the chromium plating layer exposed to the air is passivated, its potential is more positive than that of nickel.
  • the chromium plating layer will form a corrosion cell with the nickel layer when it encounters the corrosion medium. Consequently, the decorative nickel plating layer will be irregularly corroded to a large extent in extreme environments, and the chromium player may fall off due to large-area corrosion of the nickel layer.
  • microporous nickel and micro-crack nickel are applied to the bright nickel plating layer.
  • a special high stress nickel layer is plated on the bright nickel layer by using micro-crack nickel and a large number of micro-cracks will be generated by the stress after chromium is plated.
  • the microporous nickel layer diverges the corrosion current in the multi-layer nickel to prevent forming corrosion points in depth and avoid, visible corrosion.
  • the micro-crack nickel layer is separately used, the fog will be produced on the surface of the product, the brightness thereof is poor, and the trivalent chromium plating is not involved.
  • microporous nickel or micro-crack nickel is separately used, resulting in a limited improvement in anti-corrosive capacity.
  • feature for noble potential is achieved by altering the microporous nickel process to meet the requirement for anti-corrosive performance of trivalent chromium.
  • the noble potential microporous nickel could not be matched well with hexavalent chromium to satisfy anti-corrosive demands.
  • multi-layer nickel plating process for metal surface having a good anti-corrosive feature is disclosed.
  • the plating process includes (A) to metalize the surface of to plastic piece, (B) to plate bright copper, (C) to plate Semi-bright nickel, (D) to plate high sulfur nickel, (E) to plate bright nickel, (F) to plate microporous nickel, (G) to wash by water, (H) to plate bright chromium, (I) to wash by water, and (J) to dry.
  • 101705508A which discloses electroplating solution for micro-crack nickel plating and its application.
  • the main components of the micro-crack nickel electroplating solution include 180 ⁇ 260 g/L of nickel chloride, 20 ⁇ 60 ml/L of acetic acid, 80 ⁇ 120 ml/L of ELPELYT MR and 1 ⁇ 5 ml/L of 62 A.
  • the description of embodiments of the patent document is limited to hexavalent chromium plating and trivalent chromium plating is not mentioned therein.
  • the present invention provides a nickel and/or chromium plated member which significantly improves the corrosion resistance and stability of the whole member by placing a microporous nickel layer and a low potential nickel layer on the surface of the member. Meanwhile, the nickel and/or chromium plated member has good brightness and uniformity.
  • the plating layers are combined in a good way so that the member not only guarantees the bright feature of appearance of the microporous nickel layer, but also has dual corrosion resistance of the functional layer containing microporous nickel. Thereby, the member has high corrosion resistance and structural stability.
  • the nickel plated member of the invention comprises:
  • the functional layer has a low potential nickel layer and a microporous nickel layer formed on the low potential nickel layer.
  • the potential difference between the microporous nickel layer and the low potential nickel layer is in the range of 10-120 mv.
  • the low potential nickel layer includes one of a high sulfur nickel layer and a micro-crack nickel layer or a complex plating layer of the high sulfur nickel layer with the micro-crack nickel layer.
  • the potential difference between the microporous nickel layer and the low potential nickel layer is in the range of 20-100 mv.
  • the potential difference between the micro-crack nickel layer and the high sulfur nickel layer is 10-80 mv.
  • the corrosion reaches the low potential nickel layer as the potential of the micro-crack nickel layer is higher than that of the high sulfur nickel layer, the latter is first corroded as an anode plating layer and the corrosion of the micro-crack nickel layer is postponed, thereby timber enhancing the corrosion resistance.
  • the nickel-chromium plated member of the invention comprises:
  • the functional layer has a low potential nickel layer and a microporous nickel layer formed on the low potential nickel layer;
  • the decorative layer is a trivalent chromium plating layer or a hexavalent chromium plating layer.
  • the decorative layer is a trivalent chromium plating layer
  • the trivalent chromium plating layer is a trivalent black chromium plating layer or a trivalent white chromium plating layer or other types of trivalent chromium.
  • the nickel-chromium plated member of the invention comprises:
  • the functional layer has a low potential nickel layer and a microporous nickel layer formed on the low potential nickel layer;
  • the decorative layer is a trivalent chromium plating layer or a hexavalent chromium plating layer.
  • the basic layer includes one or more Semi-bright nickel layer, a high sulfur nickel layer, a bright nickel layer and a Satin nickel layer.
  • the basic layer is a complex of the Semi-bright nickel layer with the bright nickel layer or Satin nickel layer, in which the Semi-bright nickel layer is formed on the copper plating layer and the bright nickel layer or Satin nickel layer is formed on the Semi-bright nickel layer.
  • the basic layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the bright nickel layer, in which the Semi-bright nickel layer is formed on the copper plating layer, the high sulfur nickel layer is formed on the Semi-bright nickel layer and the bright nickel layer is formed on the high sulfur nickel layer.
  • the basic layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the Satin nickel layer, in which the Semi-bright nickel Semi-bright nickel layer is formed on the copper plating layer, the high sulfur nickel layer is formed on the Semi-bright nickel layer and the Satin nickel layer is formed on the high sulfur nickel layer.
  • the basic layer is a complex of the Semi-bright nickel layer, the bright nickel layer with the Satin nickel layer, in which the Semi-bright nickel layer is formed on the copper plating layer, the bright nickel layer is formed on the Semi-bright nickel layer and the Satin nickel layer is formed on the bright nickel layer.
  • the potential difference between any one of the bright nickel layer and the Satin nickel layer and the low potential nickel layer is in the range of 0-100 mv.
  • the potential difference between the Semi-bright nickel layer and the bright nickel layer and the potential difference between the Semi-bright nickel layer and the Satin nickel layer are both in the range of 100-200 mv.
  • the method for manufacturing a nickel-Chromium plated member of the invention comprises:
  • the basic layer is a complex of a Semi-bright nickel layer with a bright nickel layer or a complex of a Semi-bright nickel layer with a Satin nickel layer, in which the Semi-bright nickel layer is formed on the copper plating layer and the bright nickel layer or Satin nickel layer is formed on the Semi-bright nickel layer;
  • the functional layer is a complex of a low potential nickel layer with a microporous nickel layer, in which the low potential nickel layer is formed on the bright nickel layer or Satin nickel layer, the microporous nickel layer is formed on the low potential nickel layer, and the potential difference between the microporous nickel layer and the low potential nickel layer is 10-120 mv;
  • the decorative layer is formed on the microporous nickel layer.
  • the potential difference is controlled to be within such a range that bubbling does not tend to occur in the process of plating.
  • the plaiting layer has a reliable and firm structure and will not easily fall off.
  • the low potential nickel layer cooperates with the copper plating layer to directly plate the low potential layer onto the copper plating layer without any other plating layer doped therebetween.
  • the thickness of the microporous nickel layer is no less than 1.5 ⁇ m
  • the thickness of the micro-crack nickel layer is no less than 1.0 ⁇ m
  • the thickness of the high sulfur nickel layer is no less than 1.0 ⁇ m
  • the thickness of the Semi-bright nickel plating layer is no less than 8 ⁇ m
  • the thickness of the bright nickel plating layer is no less than 5 ⁇ m.
  • a nickel plated member comprising a substrate, a pretreatment plating layer (which could include one of a chemical nickel layer and a basic nickel layer or a composite of the chemical nickel layer with the basic nickel layer depending on the material of the substrate) formed on the whole substrate; a copper plating layer formed on the pretreatment plating layer; a functional layer formed on the copper plating layer, in which the functional layer has a low potential nickel layer and a microporous nickel layer formed on the low potential nickel layer, and the low potential nickel layer of the functional layer is formed on the copper plating layer; a basic layer could be further formed between the copper plating layer and the function layer, in which the basic layer is formed on the copper plating layer and the functional layer is formed on the basic layer; the microporous nickel layer of the functional layer is formed on the low potential nickel layer; and the potential difference between the microporous nickel layer and the low potential nickel layer is in the range of 0-120 mv.
  • the functional layer could be plated with a decorative layer depending on the requirement for appearance and other product requirements, in which the decorative layer is a chromium plating layer which is a trivalent white chromium plating layer or a trivalent black chromium plating layer or any one of other forms of trivalent or hexavalent chromium plating layers.
  • the decorative is formed on the microporous nickel plating layer of the functional layer and could have any one of a microporous configuration and a micro-crack configuration.
  • the method for manufacturing a nickel plated member of the invention comprises pretreating a surface of a substrate (in which the pretreatment is selectively conducted in accordance with the material of the substrate, including pretreatment to metal substrates and that to non-metal substrates including ABS); depositing a pretreatment plating layer over the whole substrate and forming a copper plating layer on the pretreatment plating layer; forming a low potential nickel layer of a functional layer on the copper plating layer; forming a microporous nickel layer of the functional layer on the low potential nickel layer; and forming a decorative layer on the functional layer.
  • the low potential nickel layer includes one of a high sulfur nickel layer, a micro-crack nickel layer, and a composite of the high sulfur nickel layer and the micro-crack nickel layer.
  • Chemical nickel deposition refers to the deposition of a thin film of conductive layer on the metal palladium of the surface of the substrate with catalytic activity, to facilitate subsequent electroplating of various metals.
  • both the chemical nickel layer and the basic nickel layer are present on the substrate, a thin film of conductive layer has been formed on the surface of the substrate by redox reaction in the process of chemical nickel deposition. And while the basic nickel is being plated, a layer of nickel is plated on the chemical nickel by using electrochemistry to further improve conductivity of the plating layer.
  • the copper plating layer is aimed at improving the brightness and flatness of the surface of the substrate by using the feature of copper sulphate and further improving the holistic toughness of the plating layer.
  • the copper plating layer has a better extensibility than the nickel and other metal plating layers. Consequently, the toughness and flatness of the whole plating layer could be improved after the copper sulphate layer is plated.
  • the Semi-bright nickel plating layer is aimed at plating a layer of Semi-bright nickel on the surface of the substrate.
  • the Semi-bright nickel plating layer is of a column configuration to improve the corrosion resistance of the plating layer.
  • the bright nickel plating layer is aimed at plating a layer of bright nickel on the surface of the substrate.
  • the bright nickel plating layer is of a layer configuration to improve the brightness of the plating layer.
  • the micro-crack nickel plating layer refers to an even plating layer having numberless cracks formed on the surface of the substrate which could diverge the corrosion current and reduce density of the corrosion current.
  • the microporous nickel plating layer refers to an even plating layer having numberless nonconductive particles formed on the surface of the substrate, which could further diverge the corrosion current, reduce the density of the corrosion current and fully enhance the corrosion resistance of the plating layer.
  • the pre-plated nickel plating layer has an auxiliary function, in which the boric acid is not only a stabilizer and also a blackening agent of the electroplating liquid, which could improve the covering and deep plating capacities of the electroplating liquid and enhance the compactness of the plating layer.
  • the anti-corrosive effect could be achieved in the invention when the low potential plating layer employs a single micro-crack nickel layer or a composite nickel layer of the high sulfur nickel layer with the micro-crack nickel layer.
  • the micro-crack nickel layer or microporous nickel layer of the functional layer or the combination of the micro-crack nickel layer with the microporous nickel layer could have an anti-corrosive effect and protect the substrate in that a corrosion cell is easily formed by the plating layer metal/substrate metal on the work piece.
  • the corrosion rate is controlled by the ratio of the exposed area of the plating layer metal (cathode) to that of the substrate metal (anode).
  • the cathode/anode ratio is the largest and the corrosion current is concentrated at this point. The corrosion rate becomes high and pitting corrosion could be formed inward.
  • the cathode/anode ratio is low and the corrosion current is distributed homogenously. The current on the original corrosion points is obviously reduced and the corrosion rate is largely decreased.
  • the separation among the micropores or cracks forms a discontinuous cathode of plating layer, and the plating layer becomes from a large to a small area after separation, which further limits the cathode/anode ratio.
  • the low potential nickel anti-corrosive principle is described as follows.
  • the corrosion medium when the corrosion medium is removed from the surface of the member, the corrosion will be led to spread at the nickel layer at the micropores as a highly anti-corrosive passivation layer exists on the decorative layer for example chromium layer) and micropores are existing on the surface of the chromium layer.
  • the corrosion will be divided into a number of areas because of discontinuity of the micropores, while the total corrosion amount is kept unchanged. Therefore, corrosion takes place without affecting the appearance.
  • the low potential nickel is first corroded as an anodic plating layer (that is to say, the low potential nickel layer is preferably a sacrifice layer) and corrosion in the microporous nickel is terminated, as the potential of the microporous nickel is higher than that of the low potential nickel.
  • Corrosion is led by a large number of discontinuous micro-cracks to spread in the vertical and transverse directions of cracks simultaneously.
  • the corroded area of the nickel layer will be largely increased and discontinuous. These micropores greatly diverge the corrosion current when the corrosion current is determinate, which further decreases the corrosion rate of a single point and deters the corrosion rate.
  • the chromium layer and the attachment microporous nickel layer on the appearance surface are protected to further improve the corrosion resistance of the surface of the product.
  • the low potential nickel is used as an anodic plating layer as the potential of the plating layer (e.g. copper plating layer) below the low potential nickel layer is higher than that of the low potential nickel.
  • the downward corrosion is terminated and corrosion takes place in the transverse direction in the low potential nickel, which further defers the timing for the substrate to be corroded and largely reduces the corrosion rate.
  • the present invention has the following advantages over the prior art.
  • the microporous nickel layer and the low potential nickel layer obtained by plating on the surface of the substrate in the invention have advantages such as high corrosion resistance, high hardness, high abrasion resistance, a high binding force between the plating layers and high brightness.
  • the microporous nickel layer having a high potential and the low potential nickel layer which has a multiple layers of nickel having a low potential, are used as the functional layer, and the low potential nickel layer is the sacrifice layer.
  • the microporous nickel layer having a microporous structure could diverge electrochemical corrosion micro-current, deter occurrence of corrosion and provide a support to the low potential nickel layer as the sacrifice layer by oxidizing the microporous structure to form an oxide after the low potential nickel layer is seriously corroded, which reduces the destruction rate of the plating layer of the member.
  • the low potential nickel layer used as the sacrifice layer has such a lower potential that it will be first corroded when the plating layer on the surface of the member is subject to electrochemical corrosion, and when the microporous nickel layer or micro-crack nickel layer exists, the micropores or micro-cracks could diverge the corrosion micro-current as well.
  • the micropores or micro-cracks could provide a support to the outer layer, thereby improving the firmness in terms of the material structure.
  • the invention makes use of the pore structure of the microporous nickel and micro-crack nickel, which could enhance the supporting performance of material structure and reduce the mass of the plating layers as well as the cost consumption.
  • the microporous structure could form a thin film of oxide of a large area when oxidation and corrosion take place, which greatly defers occurrence of corrosion.
  • the electroplating liquid that has little impact to environment is employed by the invention, which provides a more environment friendly plating process. Furthermore, the plating layers are combined firmly and evenly distributed and has longer use life. As such, the final product could meet the demands of the user in terms of appearance and performance. The process of the invention thus has a high competitive force on the market.
  • FIG. 1 is a schematic view of the structure of the nickel and/or chromium plated member of the invention according to one embodiment in which the base layer is a complex of the Semi-bright nickel layer with the bright nickel layer;
  • FIG. 2 is a schematic view of the structure of the nickel and/or chromium plated member of the invention according to one embodiment in which the base layer is a complex of the Semi-bright nickel layer with the Satin nickel layer;
  • FIG. 3 is a schematic view of the structure of the nickel and/or chromium plated member of the invention according to one embodiment in which the base layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the bright nickel layer;
  • FIG. 4 is a schematic view of the structure of the nickel and/or chromium plated member of the invention according to one embodiment in which the base layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the Satin nickel layer;
  • FIG. 5 is a schematic view of the structure of the nickel and/or chromium plated member of the invention according to one embodiment in which the base layer is a complex of the Semi-bright nickel layer, the bright nickel layer with the Satin nickel layer;
  • FIG. 6 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is the high sulfur nickel layer or the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer with the bright nickel layer;
  • FIG. 7 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is the high sulfur nickel layer or the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer with the Satin nickel layer;
  • FIG. 8 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is the high sulfur nickel layer or the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the bright nickel layer;
  • FIG. 9 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is the high sulfur nickel layer or the micro-crack, nickel layer and the base layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the Satin nickel layer;
  • FIG. 10 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is the high sulfur nickel layer or the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer, the bright nickel layer with the Satin nickel layer;
  • FIG. 11 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according, to one embodiment in which the low potential nickel layer is a complex layer of the high sulfur nickel layer with the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer with the bright nickel layer;
  • FIG. 12 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is a complex layer of the high sulfur nickel layer with the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer with the Satin nickel layer;
  • FIG. 13 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is a complex layer of the high sulfur nickel layer with the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the bright nickel layer;
  • FIG. 14 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is a complex layer of the high sulfur nickel layer with the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer, the high sulfur nickel layer with the Satin nickel layer;
  • FIG. 15 is a schematic view of the potential difference of the nickel and/or chromium plated member of the invention according to one embodiment in which the low potential nickel layer is a complex layer of the high sulfur nickel layer with the micro-crack nickel layer and the base layer is a complex of the Semi-bright nickel layer, the bright nickel layer with the Satin nickel layer;
  • FIG. 16 is a metallograph of the nickel plated member of the prior art subject to CASS for 72 h, in which (a) indicates the front metallograph of the sample subject to the test and (b) indicates the side (sectional) metallograph of the sample subject to the test;
  • FIG. 17 is a metallograph of the nickel plated member of the invention subject to CASS for 72 h, in which (a) indicates the front metallograph of the sample subject to the test and (b) indicates the side metallograph of the sample subject to the test;
  • FIG. 18 is a picture of the nickel plated member of the prior art subject to calcium chloride mud testing for 168 h and 336 h;
  • FIG. 19 is a picture of the nickel plated member of the invention subject to calcium chloride mud testing for 168 h and 336 h.
  • the substrate could employ metals, non-metals including ABS and other members suitable for electroplating.
  • the longitudinal coordinate axis is omitted in FIGS. 6-15 .
  • the upper or lower position of each layer of the member indicates the higher or lower potential of the said layer.
  • the multi-layer super anti-corrosive nickel-chromium plated member comprises a substrate 1 (ABS material); a pretreatment plating layer 2 having a chemical nickel layer 809 , a base nickel layer 808 and a copper plating layer 3 , in which the chemical nickel layer 809 is deposited over the whole substrate 1 , the base nickel layer 808 is deposited over the chemical nickel layer 809 and the copper plating layer 3 is formed on the base nickel layer 808 ; and a basic layer 6 formed on the copper plating layer 3 , in which the basic layer 6 has a Semi-bright nickel layer 62 and a bright nickel layer 63 , the Semi-bright nickel layer 62 is formed on the copper plating layer 3 and the bright nickel layer 63 is formed on the Semi-bright nickel layer 62 ; and a functional layer 4 formed on the bright nickel layer 63 of the basic layer 6 , in which the functional layer 4 has a low potential nickel layer 141 and a microporous nickel layer
  • the low potential nickel layer is the sacrifice layer while being subject to corrosion no matter when the low potential nickel layer is a single layer or a composite layer in this embodiment.
  • the low potential nickel layer is a composite layer of the high sulfur nickel layer with the micro-crack nickel layer
  • the potentials of the high sulfur nickel layer and the micro-crack nickel layer will be adjusted according to actual manufacturing processes, in which the high sulfur nickel layer has a higher potential or the micro-crack nickel layer has a higher potential.
  • the bright nickel layer will be corroded firstly in light of the electric corrosion priority to reduce damage to the structure of the surface layer when the low potential nickel layer is completely corroded.
  • the multi-layer super anti-corrosive nickel-chromium plated member comprises a substrate 1 (ABS material); a pretreatment plating layer 2 having a chemical nickel layer 809 , a base nickel layer 808 and a copper plating layer 3 , in which the chemical nickel layer 809 is deposited over the whole substrate 1 , the base nickel layer 808 is deposited over the chemical nickel layer 809 and the copper plating layer 3 is formed on the base nickel layer 808 ; and a basic layer 6 formed on the copper plating, layer 3 , in which the basic layer 6 has a Semi-bright nickel layer 62 and a Satin nickel layer 64 , the Semi-bright nickel layer 62 is formed on the copper plating layer 3 and the Satin nickel layer 64 is formed on the Semi-bright nickel layer 62 ; and a functional layer 4 formed on the Satin nickel layer 64 of the basic layer 6 , in which the functional layer 4 has a low potential nickel layer 141 and a microporous nickel layer
  • the low potential nickel layer is the sacrifice layer while being subject to corrosion no matter when the low potential nickel layer is a single layer or a composite layer in this embodiment.
  • the low potential nickel layer is a composite layer of the high sulfur nickel layer with the micro-crack nickel layer
  • the potentials of the high sulfur nickel layer and the micro-crack nickel layer will be adjusted according to actual manufacturing processes, in which the high sulfur nickel layer has a higher potential or the micro-crack nickel layer has a higher potential.
  • the Satin nickel layer will be corroded firstly in light of the electric corrosion priority to reduce damage to the structure of the surface layer when the low potential nickel layer is completely corroded.
  • the multi-layer super anti-corrosive nickel-chromium plated member comprises a substrate 1 (ABS material); a pretreatment plating layer 2 having a chemical nickel layer 809 , a base nickel layer 808 and a copper plating layer 3 in which the chemical nickel layer 809 is deposited over the whole substrate 1 , the base nickel layer 808 is deposited over the chemical nickel 809 and the copper plating layer 3 is formed on the base nickel layer 808 , and a basic layer 6 formed on the copper plating layer 3 , in which the basic layer 6 has a Semi-bright nickel layer 62 , a high sulfur nickel layer 61 and a bright nickel layer 63 , the Semi-bright nickel layer 62 is formed on the copper plating layer 3 , the high sulfur nickel layer 61 is formed on the Semi-bright nickel layer 62 and the bright nickel layer 63 is formed on the high sulfur nickel layer 61 ; and a functional layer 4 formed on the bright nickel layer 63 of the basic layer 6
  • the low potential nickel layer is the sacrifice layer while being subject to corrosion no matter when the low potential nickel layer is a single layer or a composite layer in this embodiment.
  • the low potential nickel layer is a composite layer of the high sulfur nickel layer with the micro-crack nickel layer
  • the potentials of the high sulfur nickel layer and the micro-crack nickel layer will be adjusted according to actual manufacturing processes, in which the high sulfur nickel layer has a higher potential or the micro-crack nickel layer has a higher potential.
  • the bright nickel layer will be corroded firstly in light of the electric corrosion priority to reduce damage to the structure of the surface layer when the low potential nickel layer is completely corroded.
  • the multi-layer super anti-corrosive nickel-chromium plated member comprises a substrate 1 (ABS material); a pretreatment plating layer 2 having a chemical nickel layer 809 , a base nickel layer 808 and a copper plating layer 3 , in which the chemical nickel layer 809 is deposited over the whole substrate 1 , the base nickel layer 808 is deposited over the chemical nickel layer 809 and the copper plating layer 3 is formed on the base nickel layer 808 and a basic layer 6 formed on the copper plating layer 3 , in which the basic layer 6 has a Semi-bright nickel layer 62 , a high sulfur nickel layer 51 and a Satin nickel layer 64 , the Semi-bright nickel layer 62 is formed on the copper plating layer 3 , the high sulfur nickel layer 61 is formed on the Semi-bright nickel layer 62 and the Satin nickel layer 64 is formed on the high sulfur nickel layer 61 ; and a functional layer 4 formed on the Satin nickel layer 64 of the basic layer 6
  • the low potential nickel layer is the sacrifice layer while being subject to corrosion no matter when the low potential nickel layer is a single layer or a composite layer in this embodiment.
  • the low potential nickel layer is a composite layer of the high sulfur nickel layer with the micro-crack nickel layer
  • the potentials of the high sulfur nickel layer and the micro-crack nickel layer will be adjusted according to actual manufacturing processes, in which the high sulfur nickel layer has a higher potential or the micro-crack nickel layer has a higher potential.
  • the Satin nickel layer will be corroded firstly in light of the electric corrosion priority to reduce damage to the structure of the surface layer when the low potential nickel layer is completely corroded.
  • the multi-layer super anti-corrosive nickel-chromium plated member comprises a substrate 1 (ABS material); a pretreatment plating layer 2 having a chemical nickel layer 809 , a base nickel layer 808 and a copper plating layer 3 , in which the chemical nickel layer 809 is deposited over the whole substrate 1 , the base nickel layer 808 is deposited over the chemical nickel layer 809 and the copper plating layer 3 is formed on the base nickel layer 808 ; and a basic layer 6 formed on the copper plating layer 3 , in which the basic layer 6 has a Semi-bright nickel Slayer 62 , a bright nickel layer 63 and a Satin nickel layer 64 , the Semi-bright nickel layer 62 is formed on the copper plating layer 3 , the bright nickel layer 63 is formed on the Semi-bright nickel layer 62 and the Satin nickel layer 64 is formed on the bright nickel layer 63 ; and a functional layer 4 formed on the Satin nickel layer 64 of the basic layer 6
  • the low potential nickel layer is the sacrifice layer while being subject to corrosion no matter when the low potential nickel layer is a single layer or a composite layer in this embodiment.
  • the low potential nickel layer is a composite layer of the high sulfur nickel layer with the micro-crack nickel layer
  • the potentials of the high sulfur nickel layer and the micro-crack nickel layer will be adjusted according to actual manufacturing processes, in which the high sulfur nickel layer has a higher potential or the micro-crack nickel layer has a higher potential.
  • the Satin nickel layer or bright nickel layer will be corroded firstly in light of the electric corrosion priority to reduce damage to the structure of the surface layer when the low potential nickel layer is completely corroded.
  • the mere difference between structural embodiments 6-10 and the structural embodiments 1-5 lies in that the low potential chromium layer 141 is a micro-crack nickel layer.
  • the mere difference between structural embodiments 11-15 and the structural embodiments 1-5 lies in that the low potential chromium layer 141 is a high sulfur nickel layer.
  • the mere difference between structural embodiments 16-30 and the structural embodiments 1-15 lies in that the decorative layer 802 is a hexavalent chromium plating layer.
  • the mere difference between structural embodiments 31-45 and the structural embodiments 1-15 lies in that the decorative layer 802 is a trivalent black chromium plating layer.
  • the mere difference between structural embodiments 46-90 and the structural embodiments 1-45 lies in that the pretreatment plating layer 2 has a base nickel layer 808 and a copper plating layer 3 , the base nickel layer 808 is deposited over the whole substrate 1 and the copper plating layer 3 is formed on the base nickel layer 808 .
  • the mere difference between structural embodiments 91-135 and the structural embodiments 1-45 lies in that the pretreatment plating layer 2 has a chemical nickel layer 809 and a copper plating layer 3 , the chemical nickel layer 809 is deposited over the whole substrate 1 and the copper plating layer 3 is formed on the chemical nickel layer 809 .
  • the substrate is cast iron material, including but not limited to, grey cast iron, white cast iron, nodular cast iron, vermicular cast iron, malleable cast iron and alloy cast iron.
  • the substrate 1 employed, in this invention could be other materials on the surface of which the copper, nickel and chromium layers could be plated.
  • the solvent used for solution of the embodiments of the invention is water including but not limited to distilled water, deionized water and water with low hardness unless particularly depicted.
  • the concentration of the solvent shall be metered on basis of unit volume or mass of solution.
  • the substrates for the members of the following embodiments preferably employ ABS materials to illustrate the methods for preparing nickel and/or chromium plated member of the invention.
  • the nickel plated member is prepared according to an embodiment of the invention as follows.
  • the surface of the substrate is pretreated by the following steps in sequence including surface deoiling, surface hydrophilic treatment, surface coarsening treatment, surface neutralization treatment, pre-immerse and surface activation treatment and surface dispergation treatment.
  • the pretreated plating layer (comprising chemically deposited nickel and base nickel, and it shall be flexibly determined according to the material of the substrate and the requirements for process and product whether to reserve the pretreatment plating layer as well as composition of the pretreatment plating layer) is deposited on the whole substrate, the chemical nickel layer and base nickel layer are formed outward in sequence on the surface of the substrate, and the copper plating layer is formed on the pretreatment plating layer (out of the base nickel layer).
  • the Semi-bright nickel layer is formed on the copper plating layer.
  • the bright nickel layer is formed on the Semi-bright nickel layer.
  • the low potential layer of the functional layer is formed on the copper plating layer, in which the lower potential nickel layer is the high sulfur nickel layer.
  • the microporous nickel layer of the functional layer is formed on the high sulfur nickel layer.
  • the decorative layer is formed on the microporous nickel layer.
  • the potential difference between the microporous nickel layer and the low potential nickel layer could be any of 20, 30, 40, 50, 60, 70, 80, 90 and 100 mv or any other value in the range of 20-100 mv. Different values could be selected from 20-100 mv, for example, 20, 40, 60, 80 and 100 mv, as the potential difference between the microporous nickel layer and the low potential nickel layer in each of the corresponding embodiments 1-5.
  • the potential difference between the microporous nickel layer and the low potential nickel layer could also be the same as each other in all the embodiments.
  • the potential difference between the bright nickel layer and the low potential nickel layer could be any of 0, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100 mv or any other value in the range of 20-100 mv. Different values could be selected from 0-100 mv, for example, 0, 30, 60, 80 and 100 mv, as the potential difference between the bright nickel layer and the low potential nickel layer in each of the corresponding embodiments 1-5.
  • the potential difference between the bright nickel layer and the low potential nickel layer could also be the same as each other in all the embodiments.
  • the potential difference between the Semi-bright nickel layer and the bright nickel layer could be any of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 and 200 mv or any other value in the range of 100-200 mv. Different values could be selected from 100-200 mv, for example, 100, 120, 150, 180 and 200 mv, as the potential difference between the Semi-bright nickel layer and the bright nickel layer in each of the corresponding embodiments 1-5.
  • the potential difference between the Semi-bright nickel layer and the bright nickel layer could also be the same as each other in all the embodiments.
  • the method for electroplating nickel on the said nickel-chromium plated member comprises the following steps:
  • Embodiment Component 1 2 3 4 5 NaOH (g/L) 20 35 30 40 50 Na 2 CO 3 (g/L) 42 36 32 25 18 Surface Active Agent (g/L) 2 3 2 1 3 Na 2 SiO 3 (g/L) 30 20 40 25 10
  • Embodiment Component 1 2 3 4 5 H 2 SO 4 (g/L) 80 40 20 50 100 Surface Treatment Agent(ml/L) 1.5 1.0 2 1.2 0.5
  • Embodiment Component 1 2 3 4 5 Hydrochloric Acid (g/L) 30 100 80 60 50 Hydrazine Hydrate (ml/L) 60 30 15 20 50
  • Embodiment Component 1 2 3 4 5 SnCl 2 (ppm) 40 30 20 60 50 SnCl 2 (g/L) 7.0 5.8 4.5 3.7 2.5 Hydrochloric Acid (ml/L) 180 200 230 260 280
  • Embodiment Component 1 2 3 4 5 H 2 SO 4 (g/L) 60 40 80 50 100
  • the aforesaid preliminary pretreatment processes for the substrate of ABS material shall also be applicable to the pretreatment processes for the substrate of other non-metal materials.
  • the subsequent plating process could be carried out immediately after the deoiling process in the surface deoiling treatment.
  • specific processes are also applicable to the corresponding processes in the fundamental preliminary pretreatment processes for the substrate of non-metal materials.
  • Embodiment Component 1 2 3 4 5 Ni 2 SO 4 —6H 2 O (g/L) 200 300 280 230 250 NiCl 2 —6H 2 O (g/L) 40 35 45 38 50 Boric Acid H 3 BO 3 (g/L) 50 48 42 40 35 Semi-bright nickel Primary 3.0 6.0 4.0 7.0 5.0 Brightening Agent (ml/L) Semi-bright nickel 1.0 0.8 0.6 0.3 0.5 Secondary Brightening Agent (ml/L) Potential Difference 0.3 0.4 0.1 0.5 0.6 Adjusting Agent (ml/L) Wetting Agent (ml/L) 2.0 3.0 2.5 1.5 1.0
  • Embodiment Component 1 2 3 4 5 Ni 2 SO 4 —6H 2 O (g/L) 240 360 280 330 350 NiCl 2 —6H 2 O (g/L) 45 35 65 55 50 Boric Acid H 3 BO 3 (g/L) 65 55 45 60 35 Bright Nickel Softening 8 10 12 15 9 Agent (ml/L) Bright Nickel Brightening 10 8 6 5 7 Agent A (ml/L) Bright Nickel Primary 2.0 3.0 2.5 1.5 1.8 Brightening Agent (ml/L) Wetting Agent (ml/L) 3.0 2.5 2.0 1.0 1.5
  • Embodiment Component 1 2 3 4 5 Ni 2 SO 4 —6H 2 O (g/L) 250 350 280 300 320 NiCl 2 —6H 2 O (g/L) 60 50 35 40 45 Boric Acid H 3 BO 3 (g/L) 35 65 50 45 55 High Sulfur Adding Agent 8 6 10 3 5 (ml/L) Wetting Agent (g/L) 28 12.5 18.7 28 24
  • the mere difference between the preparing embodiments 6-10 and the preparing embodiments 1-5 lies in that the low potential nickel layer is a micro-crack layer and the electroplating liquid as illustrated in Table 20 is applied for plating the micro-crack nickel layer.
  • the other parameters for the process for plating micro-crack nickel are illustrated in Table 21.
  • Embodiment Component 6 7 8 9 10 NiCl 2 —6H 2 O (g/L) 180 240 260 200 220 Acetic Acid (g/L) 20 30 40 10 25 PN-1A (g/L) 50 40 90 60 70 PN-2A (g/L) 2 4 3 5 1 Wetting Agent (ml/L) 3 2 4 1 5
  • the mere difference between the preparing embodiments 11-15 and the preparing embodiments 1-5 lies in that the low potential nickel layer contains a complex of the high sulfur nickel layer (the electroplating liquid for each embedment is illustrated in Table 15 in sequence correspondingly) and the micro-crack nickel layer (the electroplating liquid for each embedment is illustrated in Table 20 in sequence correspondingly).
  • the potential difference between the micro-crack nickel layer and the high sulfur nickel layer could be any of 10, 20, 30, 40, 50, 60, 70 and 80 mv or any other value in the range of 10-80 mv.
  • Different values could be selected from 10-80 mv, for example, 10, 20, 40, 60 and 80 mv, as the potential difference between the micro-crack nickel layer and the high sulfur nickel layer in each of the corresponding embodiments 11-15.
  • the potential difference between the micro-crack nickel layer and the high sulfur nickel layer could also be the same as each other in all the embodiments.
  • the mere difference between the preparing embodiments 16-30 and the preparing embodiments 1-15 lies in that the bright nickel layer is replaced with a Satin nickel layer and the electroplating liquid as illustrated in Table 22 is applied for plating the Satin nickel layer (a random number is used to indicate the embodiments).
  • Embodiment Component 1 2 3 4 5 Ni 2 SO 4— 6H 2 O (g/L) 250 350 280 330 350 NiCl 2— 6H 2 O (g/L) 45 35 60 55 50 Boric Acid H 3 BO 3 (g/L) 65 55 45 60 35 Auxiliary Additive (ml/L) 12 10 20 15 5 Satin Nickel Forming Agent 0.2 0.3 0.6 0.5 0.4 (ml/L)
  • the mere difference between the preparing embodiments 31-60 and the preparing embodiments 1-30 lies in that the trivalent white chromium layer in the decorative layer is replaced with trivalent black chromium layer and the electroplating liquid as illustrated in Table 23 is applied for plating the trivalent black chromium layer correspondingly (a random number is used to indicate the embodiments).
  • Embodiment Component 1 2 3 4 5 CrCl 3— 6H 2 O (g/L) 150 200 180 250 220 Oxalic Acid (g/L) 2 3 4 5 3 Ammonium Acetate (g/L) 8 5 3 6 10 Ammonium Chloride (g/L) 40 25 35 20 30 Boric Acid (g/L) 20 41 30 35 25 Additive Agent (ml/L) 2.5 0.5 2.0 1.5 3.0
  • the mere difference between the preparing embodiments 61-90 and the preparing embodiments 1-30 lies in that the trivalent white chromium layer in the decorative layer is replaced with hexavalent chromium layer and the electroplating liquid as illustrated in Table 24 is applied for plating the hexavalent chromium layer correspondingly (a random number is used to indicate the embodiments).
  • Embodiment Component 1 2 3 4 5 Chromium Trioxide (g/L) 320 260 280 300 360 Sulphuric Acid (ml/L) 0.5 2 1 3 2.5 Decorative Chromium 2.0 1.0 3.0 2.0 3.0 Brightening Agent (g/L) Chromium Fog Inhibiting 0.2 0.3 0.3 0.4 0.4 Agent (ml/L)
  • PN-1A and PN-2A are both products available on the market by Atotech (China) Chemicals Ltd.
  • the substrate employed, in the invention could be made from materials including C, PP, PVC, PET, bakelite and metallic materials.
  • the pretreatment plating layer could be existing or not existing depending on the performance of actual materials and processing requirements.
  • FIG. 17 indicates a corrosion state of the nickel plated member according to one embodiment of the invention subject to CASS test for 72 h.
  • FIG. 16 indicates a corrosion state of the nickel plated member of the prior art subject to CASS test for 72 h (under the same experimental conditions). Comparing FIG. 17 with FIG. 16 , it could be directly seen that the sample of the prior art has plating layers peeled off to a large extent and corrosion gaps 21 generated after corrosion, and the quality of the plating layer of the product is seriously affected. It could be viewed from FIG. 3 that the nickel plated sample of the invention has a certain number of surface micropores 31 on its surface and only small corrosion holes 32 exist in the section. Neither the surface micropores nor the corrosion holes produced in the sacrifice layer could destroy the plating layer of the member. And the use and appearance of the product will not be influenced either.
  • FIG. 18 and FIG. 19 respectively indicate the corrosion state of the surface of the nickel plated member sample of the prior art and that of the surface of the nickel plated member sample according to one embodiment of the invention subject to calcium chloride mud testing for 336 h, 336 h and 168 h, in which the circular parts refer to the areas subject to the test. It could be determined from the figures that the surfaces of the nickel plated member of the prior art are subject to corrosion to different degrees, and the samples of the invention are slightly corroded and no color change is involved. As such, the nickel plated member obtained by the invention has better stability and corrosion resistance for the plating layer, and the nickel plated member is more durable and has more aesthetic appearance.

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